Highly active trimetallic materials using short-chain alkyl quaternary ammonium compounds

ABSTRACT

A highly active trimetallic mixed transition metal oxide material has been developed. The material may be sulfided to generate metal sulfides which are used as a catalyst in a conversion process such as hydroprocessing. The hydroprocessing may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from U.S. Provisional Application No.62/608,378 filed Dec. 20, 2017, the contents of which cited applicationare hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to a new catalyst or catalyst precursor. Moreparticularly this invention relates to a novel mixed transition metaloxide and its use as a catalyst or catalyst precursor such as ahydrocarbon conversion catalyst or catalyst precursor or specifically ahydroprocessing catalyst or catalyst precursor. The hydroprocessing mayinclude hydrodenitrification, hydrodesulfurization, hydrodemetallation,hydrodesilication, hydrodearomatization, hydroisomerization,hydrotreating, hydrofining, and hydrocracking.

BACKGROUND

Currently there are two main drivers for refiners to invest inhydroprocessing technology. The first being environmental regulationsimposing more stringent specifications on fuels including gasoline,diesel, and even fuel oils. For example, permitted sulfur and nitrogenlevels in fuels are significantly lower than one decade ago. A seconddriving force is the quality of crude oils. More refineries are facingcrude oils containing higher concentrations of sulfur and nitrogencompounds which are difficult to process or remove by conventionalprocesses. Without new technology, refiners resort to increasing theseverity of hydrotreating processes either by increasing the reactortemperatures or decreasing space velocity through the reactor.Increasing reactor temperature has the drawback of shortening catalystlifetime. Decreasing space velocity, through increasing reactor size ordecreasing feed flow rates, has the drawback of overhauling the reactorsor significantly reducing production rates. Therefore, a highly activehydroprocessing catalyst is needed. A highly active hydroprocessingcatalyst helps the refiners meet the stringent fuel sulfur and nitrogenlimitations without significant investment in reactors and equipment andwhile maintaining production rates.

In the early 2000s, unsupported, also called “bulk”, hydrotreatingcatalysts were applied in commercial hydrotreating processes. Thesecatalysts were claimed to have several times more activity thanconventional supported NiMo or CoMo hydrotreating catalysts based on thesame loading volumes. However, to achieve the high activity, theunsupported hydrotreating catalysts often contained significantly moremetal content than the conventional supported hydrotreating catalysts.Increased metal content means the cost of the catalyst is alsoincreased. Thus, there is a need in the industry for an unsupportedcatalyst with better intrinsic activity per mass. An unsupportedcatalyst with higher intrinsic activity per mass will require less metalloading to achieve the same activity as the unsupported catalyst withless intrinsic activity at the same loading volumes.

U.S. Pat. No. 6,156,695 described a Ni—Mo—W mixed metal oxide material.The XRD pattern of this material was shown to be largely amorphous withonly two crystalline peaks, the first at d=2.53 Angstroms and the secondat d=1.70 Angstroms. U.S. Pat. No. 6,534,437 described a process forpreparing a catalyst comprising bulk catalyst particles having at leastone Group VIII non-noble metal and at least two Group VIB metals. Themetal components were stated to be at least partly in the solid stateduring the material synthesis reaction with solubility of less than 0.05mol/100 ml water at 18° C. U.S. Pat. No. 7,544,632 showed a bulkmulti-metallic catalyst composition containing quaternary ammonium,[CH₃(CH₂)_(d)N(CH₃)₃], where d is an integer from about 10 to about 40.U.S. Pat. No. 7,686,943 described a bulk metal catalyst comprising metaloxidic particles containing niobium as a Group V metal, a single GroupVIB metal, and a single Group VIII metal. U.S. Pat. No. 7,776,205described a bulk metal catalyst comprising a single Group VIB metal, aGroup VB metal, and a Group VIII metal.

U.S. Pat. No. 8,173,570 showed co-precipitation to form at least a metalcompound in solution selected from Group VIII, at least two Group VIBmetal compounds in solution, and at least one organic oxygen containingchelating ligand in solution. The organic oxygen containing ligand hasan LD50 rate larger than 700 mg/kg. U.S. Pat. No. 7,803,735 showedforming an unsupported catalyst precursor by co-precipitating at leastone of a Group VIB metal compound, at least a metal compound selectedfrom Group VIII, Group IIB, Group IIA, Group IVA, and combinationsthereof, and at least one of an organic oxygen-containing ligand.

CN 101306374 described a catalyst of at least one Group VIII metal, atleast two Group VIB metals and an organic additive. The organic additiveis selected from organic ammonium compounds with the formula ofC_(n)H_(2n+1)N(Me)₃X or (C_(n)H_(2n+1))₄NX where n=2-20 and

X denotes Cl, Br, or OH. The XRD provided shows peaks at d=11.30+/−1.5Angstroms, d=4.15+/−0.5 Angstroms, d=2.60+/−0.5 Angstroms, andd=1.53+/−0.5 Angstroms.

Unsupported NiZnMoW materials have been discussed in Applied CatalysisA: General 474 (2014) page 60-77. The material was synthesized in twosteps. The first step prepared layered NiZn hydroxides. The second stepprepared the NiZnMoW material via the reaction of layered NiZn hydroxideand solution containing MoO₄ ²⁻ and WO₄ ²⁻.

There is a need for new materials to meet increasing demands ofconversion processes including the need for catalysts with higherintrinsic activity per mass. The material disclosed herein is unique andnovel in elemental composition as compared to previous materials.

SUMMARY OF THE INVENTION

A novel mixed transition metal oxide material has been produced andoptionally sulfided, to yield an active catalyst such as ahydroprocessing catalyst. The novel mixed transition metal oxidematerial has the formula:

(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)O^(e) _(q)

where: M_(I) is a metal or a mixture of metals selected from Group VIII(IUPAC Groups 8, 9, and 10); M_(II) is a metal selected from Group VIB(IUPAC Group 6); M_(III) is a metal selected from Group VIB (IUPAC Group6) which is different from M_(II); a, b, c, and e are the valence stateof M_(I), M_(II), M_(III), and O; m, n, o, and q are the mole ratio ofM_(I), M_(II), M_(III), and O, wherein m/(n+o) is from 1/10 to 10/1,wherein n/o>0 and 0≤o/n≤100, wherein q is greater than 0; and wherein a,b, c, e, m, n, o, and q satisfy the equation:

a*m+b*n+c*o+e*q=0

the material further characterized by an x-ray diffraction patterncomprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°.

Another embodiment involves a method of making a mixed transition metaloxide material having the formula:

(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)O^(c) _(q)

where: M_(I) is a metal or a mixture of metals selected from Group VIII(IUPAC Groups 8, 9, and 10); M_(II) is a metal selected from Group VIB(IUPAC Group 6); M_(III) is a metal selected from Group VIB (IUPAC Group6) which is different from M_(II); a, b, c, and e are the valence stateof M_(I), M_(II), M_(III), and O; m, n, o, and q are the mole ratio ofM_(I), M_(II), M_(III), and O, wherein m/(n+o) is from 1/10 to 10/1,wherein n/o>0 and 0≤o/n≤100, wherein q is greater than 0; and wherein a,b, c, e, m, n, o, and q satisfy the equation:

a*m+b*n+c*o+e*q=0

the material further characterized by an x-ray diffraction patterncomprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°; wherein the method comprises: forming a reaction mixturecontaining a protic solvent, sources of M_(I), M_(II), and M_(III), abasic solution, and at least one short-chain alkyl quaternary ammoniumhalide compound having the formula [R1 R2 R3 R4-N]X, where R1, R2, R3and R4 are alkyl radicals having 1 to 6 carbon atoms such as methyl,ethyl, propyl, butyl, pentyl, and hexyl, and where R1, R2, R3 and R4 canbe the same or different from each other; mixing the reaction mixture;reacting the reaction mixture at a temperature from about 25° C. toabout 200° C. for a period of time from about 30 minutes to 200 hours togenerate the mixed transition metal oxide material; and recovering themixed transition metal oxide material. The recovery may be by decanting,filtration or centrifugation, with or without washing of the recoveredproduct with a protic solvent. A binder may be incorporated during thereaction or may be added to the recovered material. The binder isselected from aluminas, silicas, alumina-silicas, titanias, zirconias,natural clays, synthetic clays, and mixtures thereof. The recoveredmixed transition metal oxide material may be sulfided. The pH of thereaction mixture may be adjusted using an acidic or basic solution. Thereaction is conducted under atmospheric pressure or autogenous pressure.Forming the reaction mixture and the mixing may occur at the same time.

Yet another embodiment involves a conversion process comprisingcontacting a sulfiding agent with a material to generate metal sulfideswhich are contacted with a feed at conversion conditions to generate atleast one product, the material comprising a mixed transition metaloxide material having the formula:

(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)O^(c) _(q)

where: M_(I) is a metal or a mixture of metals selected from Group VIII(IUPAC Groups 8, 9, and 10); M_(II) is a metal selected from Group VIB(IUPAC Group 6); M_(III) is a metal selected from Group VIB (IUPAC Group6) which is different from M_(II); a, b, c, and e are the valence stateof M_(I), M_(II), M_(III), and O; m, n, o, and q are the mole ratio ofM_(I), M_(II), M_(III), and O, wherein m/(n+o) is from 1/10 to 10/1,wherein n/o>0 and 0≤o/n≤100, wherein q is greater than 0; and wherein a,b, c, e, m, n, o, and q satisfy the equation:

a*m+b*n+c*o+e*q=0

the material further characterized by an x-ray diffraction patterncomprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°.

The conversion process may be a hydrocarbon conversion process. Theconversion process may be hydroprocessing. The conversion process may behydrodenitrification, hydrodesulfurization, hydrodemetallation,hydrodesilication, hydrodearomatization, hydroisomerization,hydrotreating, hydrofining, or hydrocracking. The mixed transition metaloxide material may be present in a mixture with at least one binder andwherein the mixture comprises up to about 80 wt % binder.

Additional features and advantages of the invention will be apparentfrom the description of the invention and claims provided herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the X-ray diffraction pattern of the transition metal oxidematerial described herein and prepared as described in Examples 1 to 4.

FIG. 2 is a portion of the X-ray diffraction pattern of FIG. 1 furthershowing peak deconvolution between 2θ (°) of 45-75°.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a novel mixed transition metal oxidematerial, a process for preparing the material, and a process using thematerial. The material has an empirical formula:

(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)O^(c) _(q)

where: M_(I) is a metal or a mixture of metals selected from Group VIII(IUPAC Groups 8, 9, and 10); M_(II) is a metal selected from Group VIB(IUPAC Group 6); M_(III) is a metal selected from Group VIB (IUPAC Group6) which is different from M_(II); a, b, c, and e are the valence stateof M_(I), M_(II), M_(III), and O; m, n, o, and q are the mole ratio ofM_(I), M_(II), M_(III), and O, wherein m/(n+o) is from 1/10 to 10/1,wherein n/o>0 and 0≤o/n≤100, wherein q is greater than 0; and wherein a,b, c, e, m, n, o, and q satisfy the equation:

a*m+b*n+c*o+e*q=0

the material further characterized by an x-ray diffraction patterncomprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°.

Patterns presented herein in tabular form were obtained using standardx-ray powder diffraction techniques. The radiation source was ahigh-intensity, x-ray tube operated at 45 kV and 35 mA. The diffractionpattern from the copper K-alpha radiation was obtained by appropriatecomputer based techniques. Powder samples were pressed flat into a plateand continuously scanned from 3° and 70° (20). Interplanar spacings (d)in Angstrom units were obtained from the position of the diffractionpeaks expressed as θ, where θ is the Bragg angle as observed fromdigitized data. As will be understood by those skilled in the art thedetermination of the parameter 2θ is subject to both human andmechanical error, which in combination can impose an uncertainty ofabout ±0.4° on each reported value of 2θ. This uncertainty is alsotranslated to the reported values of the d-spacings, which arecalculated from the 2θ values. The intensity of each peak was determinedby the peak height after subtracting background. To prevent errors inpeak deconvolution, the background is taken to be linear in the rangedelimiting the broad diffraction features, 6-2 Å. I_(o) is the intensityof the peak at 2θ of 34.5-36.5°. I/I_(o) is the ratio of the intensityof a peak to I_(o). In terms of 100(I/I_(o)), the above designations aredefined as:

vw=0-5, w=5-20, m=20-60, s=60-80, and vs=80-100. It is known to thoseskilled in the art, the noise/signal ratio in XRD depends on scanconditions. Sufficient scan time is required to minimize noise/signalratio to measure peak intensities.

Although M_(I) is a metal or a mixture of metals selected from GroupVIII (IUPAC Groups 8, 9, and 10), in one embodiment M_(I) may beselected from Fe, Co, Ni, and any mixture thereof. Although M_(II) is ametal selected from Group VIB (IUPAC Group 6) in one embodiment, M_(II)is selected from Cr, Mo, and W. Although M_(III) is a metal selectedfrom Group VIB (IUPAC Group 6) which is different from M_(II), in oneembodiment M_(III) is selected from Cr, Mo, and W so long as M_(III) isdifferent from M_(II).

The novel mixed transition metal oxide material can be prepared byco-precipitation by mixing, in a protic solvent, sources of thetransition metals with basic solution and short chain alkyl quaternaryammonium halide compounds. The term “metal” as used herein is meant torefer to the element and not meant to necessarily indicate a metallicform.

Sources of M_(I) include, but are not limited to, the respective halide,sulfide, acetate, nitrate, carbonate, sulfate, oxalate, thiols,hydroxide salts, and oxides of M_(I). Specific examples of sources ofM_(I) include, but are not limited to, nickel chloride, nickel bromide,nickel nitrate, nickel acetate, nickel carbonate, nickel hydroxide,cobalt chloride, cobalt bromide, cobalt nitrate, cobalt acetate, cobaltcarbonate, cobalt hydroxide, cobalt sulfide, nickel chloride, cobaltoxide, nickel bromide, nickel nitrate, nickel acetate, nickel carbonate,nickel hydroxide, nickel sulfide, nickel oxide, iron acetate, ironoxalate, iron nitrate, iron chloride, iron bromide, iron sulfate, ironcarbonate, iron acetate, iron oxalate, iron sulfide, iron oxide, and anymixture thereof

Sources of M_(II) include, but are not limited to, the respective oxidesof M_(III), sulfides of M_(III), halides of M_(II), molybdates,tungstates, thiolmolybdates, and thioltungstates. Specific examples ofsources of M_(II) include, but are not limited to, molybdenum trioxide,ammonium dimolybdate, ammonium thiomolybdate, ammonium heptamolybdate,sodium dimolybdate, sodium thiomolybdate, sodium heptamolybdate,potassium dimolybdate, potassium thiomolybdate, potassiumheptamolybdate, molybdenum sulfide, tungsten trioxide, tungstic acid,tungsten oxytetrachloride, tungsten hexachloride, hydrogen tungstate,ammonium ditungstate, sodium ditungstate, ammonium metatungstate,ammonium paratungstate, sodium ditungstate, sodium ditungstate, sodiummetatungstate, sodium paratungstate, and any mixture thereof.

Sources of M_(III) include, but are not limited to, the respectiveoxides of M_(III), sulfides of M_(III), halides of M_(III), molybdates,tungstates, thiolmolybdates, and thioltungstates. Specific examples ofsources of M_(III) include, but are not limited to, molybdenum trioxide,ammonium dimolybdate, ammonium thiomolybdate, ammonium heptamolybdate,sodium dimolybdate, sodium thiomolybdate, sodium heptamolybdate,potassium dimolybdate, potassium thiomolybdate, potassiumheptamolybdate, molybdenum sulfide, tungsten trioxide, tungstic acid,tungsten oxytetrachloride, tungsten hexachloride, hydrogen tungstate,ammonium ditungstate, sodium ditungstate, ammonium metatungstate,ammonium paratungstate, sodium metatungstate, sodium paratungstate, andany mixtures thereof.

Specific examples of basic solutions include, but are not limited to,ammonia-water (NH3.H2O), sodium hydroxide (NaOH), potassium hydroxide(KOH), tetramethylammonium hydroxide (TMAOH), tetrapropylammoniumhydroxide (TPAOH), tetrabutylammonium hydroxide (TBAOH) and any mixturesthereof.

The short-chain alkyl quaternary ammonium halide compound is selectedfrom compounds having the formula [R1 R2 R3 R4-N]X, where R1, R2, R3 andR4 are alkyl radicals having from 1 to 6 carbon atoms such as methyl,ethyl, propyl, butyl, pentyl, and hexyl, and R1, R2, R3 and R4 can bethe same or different from each other. In a specific embodiment, X isselected from F, Cl, Br, and I. Specific examples of short-chain alkylquaternary ammonium halide compounds include, but are not limited to,tetra methyl ammonium chloride, tetra methyl ammonium bromide, tetraethyl ammonium chloride, tetra ethyl ammonium bromide, tetra propylammonium chloride, tetra propyl ammonium bromide, tetra butyl ammoniumchloride, tetra butyl ammonium bromide, tetra pentyl ammonium chloride,tetra pentyl ammonium bromide, tri-butyl methyl ammonia chloride,tri-butyl methyl ammonium bromide, tri-propyl methyl ammonium chloride,tri-propyl methyl ammonium bromide, tri-ethyl methyl ammonium chloride,tri-ethyl methyl ammonium bromide, di-propyl di-methyl ammoniumchloride, di-propyl di-methyl ammonium bromide, butyl tri-methylammonium chloride, butyl tri-methyl ammonium bromide, and any mixturethereof.

The material of the invention has unique features characterized by X-raypowder diffraction (XRD) pattern. The material may be characterized byan x-ray diffraction pattern comprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°. Additional peaks may comprise 2θ (°) 18-21, d (Å) of4.227-4.924, with 100(I/I_(o)) of vw to w; 2θ (°) 21-23, d (Å) of3.864-4.227, with 100(I/I_(o)) of m to s; 2θ (°) 30-32, d (Å) of2.795-2.976, with 100(I/I_(o)) of m to s. In one embodiment, the XRDpattern of the material comprises a peak between 2θ of 21° and 23°; apeak between 2θ of 34.5° and 36.5°; a peak between 2θ of 53° and 55° apeak between 2θ of 55° and 58° with the full width at half maximum(FWHM) larger than 3°; and a peak between 2θ of 62.8° and 63.8°.

The material of this invention can be prepared by co-precipitation byforming a reaction mixture in a protic solvent comprising the sources oftransition metals, basic solution, and at least one short-chain alkylquaternary ammonium halide compound. Suitable protic solvents includewater and alcohols such as ethanol, isopropanol, butanol, and glycol.Suitable basic solutions are discussed above. The reaction mixture maybe formed by adding the components of the reaction mixture in any orderand in any combination and as a variety of solutions. In one embodiment,the sources of M_(I), M_(II), and M_(III), may be in one or moresolutions prior to forming the reaction mixture. In one embodiment,sources or solutions of M_(I), M_(II), and M_(III) may be mixed withprotic solvent, basic solutions, a short-chain alkyl quaternary ammoniumhalide solution, or any of the above prior to combination to form thereaction mixture. In another embodiment, the prepared M_(I), M_(II), andM_(III) solutions can be added into protic solution and basic solutionand a short-chain alkyl quaternary ammonium halide solution added to theprotic solution to form the reaction mixture. In yet another embodiment,solutions of sources of M_(I), M_(II), and M_(III) in protic solvent canbe added simultaneously together with the basic solution and ashort-chain alkyl quaternary ammonium halide solution to form thereaction mixture.

Depending upon the metal sources selected, the pH of the reactionmixture may be adjusted to an acidic or a basic regime. The pH of themixture may be adjusted through the addition of a base such as NH₄OH,quaternary ammonium hydroxides, amines, and the like, or converselythrough the addition of a mineral acid such as nitric acid, hydrochloricacid, sulfuric acid, hydrofluoric acid, or an organic acid such ascitric acid or malic acid, depending upon reactive sources of metals. Inone embodiment, the pH does not need to be adjusted.

During or after mixing the components including, the protic solvent, thebasic solution, the short-chain alkyl quaternary ammonium halidesolution, and sources of M_(I), M_(II), and M_(III), the reactionmixture is reacted at temperature in the range of about 25° C. to about200° C., or from about 60° C. to about 180° C., or from about 80° C. toabout 150° C. in a sealed autoclave reactor or in a reactor open toambient pressure. The sealed autoclave reactor or the reactor open toambient pressure can be equipped with a stirring device to mix thereaction mixture. In another embodiment, the sealed autoclave or thereactor open to the ambient pressure does not have a stirring device andthe reaction is conducted at a static state unless the temperature ofthe reaction mixture is higher than boiling point of the mixture,causing autonomous stirring by the boiling of the reaction mixture. Inembodiment where a reactor open to ambient pressure is employed, areflux device can be optionally attached to the reactor to avoid solventloss when the reaction temperature is close to or above the boilingtemperature of the reaction mixture.

The reaction time may range from about 0.5 to about 200 h, or 0.5 h toabout 100 h, or from about 1 h to about 50 h, or from about 2h to about24h. Optionally, the reaction mixture may be mixed continuously orintermittently during the reaction. In one embodiment, the reactionmixture is mixed every few hours. During reaction, the pH of thereaction mixture can vary autonomously due to the thermal decompositionof basic compounds at elevated reaction temperatures, or the pH of thereaction mixture may be adjusted manually by adding acidic or basiccompounds into the reaction mixture, depending on the desired pH. The pHof the mixture may be adjusted through the addition of a base such asNH4OH, quaternary ammonium hydroxides, amines, and the like, orconversely though the addition of an acid such as a mineral acid such asnitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid, or anorganic acid such as citric acid or malic acid. In one embodiment, thepH does not need to be adjusted. As the reaction progresses, a slurry isformed. At the end of the reaction time, the pH of the slurry may befrom about 6 to about 9, or from about 6 to about 8.5, or from about 6to about 7.5. The slurry may need to be adjusted by adding acidic orbasic compounds into the slurry to obtain the desired final pH. Themixed transition metal oxide material is recovered from the slurry.

In a specific embodiment, the mixed transition metal oxide material maybe present in a composition along with a binder, where the binder maybe, for example, silicas, aluminas, silica-aluminas, titanias,zirconias, natural clays, synthetic clays, and mixtures thereof. Theselection of binder includes but is not limited to, anionic and cationicclays such as hydrotalcites, pyroaurite-sjogrenite-hydrotalcites,montmorillonite and related clays, kaolin, sepiolites, silicas, aluminassuch as (pseudo) boehomite, gibbsite, flash calcined gibbsite,eta-alumina, zicronica, titania, alumina coated titania, silica-alumina,silica coated alumina, alumina coated silicas and mixtures thereof, orother materials generally known as particle binders in order to maintainparticle integrity. These binders may be applied with or withoutpeptization. The binder may be added to the bulk mixed transition metaloxide material, or may be incorporated during synthesis. The amount ofbinder may range from about 1 to about 80 wt % of the finishedcomposition, or from about 1 to about 30 wt % of the finishedcomposition, or from about 5 to about 26 wt % of the finishedcomposition. The binder may be chemically bound to the mixed transitionmetal oxide material, or may be present in a physical mixture with thenovel mixed transition metal oxide material. The mixed transition metaloxide material maybe extruded or pelletized with or without a binder.

At least a portion of the mixed transition metal oxide material, with orwithout a binder, or before or after inclusion of a binder, can besulfided in situ in an application or pre-sulfided to form metalsulfides which in turn are used in an application. The sulfidation maybe conducted under a variety of sulfidation conditions such as throughcontact of the mixed transition metal oxide material with a sulfurcontaining stream or feedstream as well as the use of a gaseous mixtureof H₂S /H₂. The sulfidation of the mixed transition metal oxide materialis performed at elevated temperatures, typically ranging from 50 to 600°C., or from 150 to 500° C., or from 250 to 450° C. The sulfiding stepcan take place at a location remote from other synthesis steps, remotefrom the location of the application where the mixed transition metaloxide material will be used, or remote from both the location ofsynthesis and remote from location of use. The materials resulting fromthe sulfiding step are referred to as metal sulfides which can be usedas catalysts in conversion processes.

As discussed, at least a portion of the mixed transition metal oxidematerial of this invention can be sulfided and the resulting metalsulfides used as catalysts in conversion processes such as hydrocarbonconversion processes. Hydroprocessing is one class of hydrocarbonconversion processes in which the mixed transition metal oxide materialis useful as a catalyst. Examples of specific hydroprocessing processesare well known in the art and include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking. In one embodiment, a conversion process comprisescontacting the mixed transition metal oxide material with a sulfidingagent to generate metal sulfides which are contacted with a feed streamat conversion conditions to generate at least one product.

The operating conditions of the hydroprocessing processes listed abovetypically include reaction pressures from about 2.5 MPa to about 17.2MPa, or in the range of about 5.5 to about 17.2 MPa, with reactiontemperatures in the range of about 245° C. to about 440° C., or in therange of about 285° C. to about 425° C. Contact time for the feed andthe active catalyst, referred to as liquid hourly space velocities(LHSV), should be in the range of about 0.1 h⁻¹ to about 10 h⁻¹, orabout 2.0 h⁻¹ to about 8.0 h⁻¹. Specific subsets of these ranges may beemployed depending upon the feedstock being used. For example, whenhydrotreating a typical diesel feedstock, operating conditions mayinclude from about 3.5 MPa to about 8.6 MPa, from about 315° C. to about410° C., from about 0.25/h to about 5/h, and from about 84 Nm³ H₂/m³ toabout 850 Nm³ H₂/m³ feed. Other feedstocks may include gasoline,naphtha, kerosene, gas oils, distillates, and reformate.

Examples are provided below to describe the invention more completely.These examples are only by way of illustration and should not beinterpreted as a limitation of the broad scope of the invention, whichis set forth in the claims.

Patterns presented herein (may be in tabular form) were obtained usingstandard x-ray powder diffraction techniques. The radiation source was ahigh-intensity, x-ray tube operated at 45 kV and 35 mA. The diffractionpattern from the copper K-alpha radiation was obtained by appropriatecomputer based techniques. Powder samples were pressed flat into a plateand continuously scanned from 3° and 70° (2θ). Interplanar spacings (d)in Angstrom units were obtained from the position of the diffractionpeaks expressed as θ, where θ is the Bragg angle as observed fromdigitized data. Intensities were determined from the integrated area ofdiffraction peaks after subtracting background, “I_(o)” being theintensity of the strongest line or peak, and “I” being the intensity ofeach of the other peaks. As will be understood by those skilled in theart the determination of the parameter 2θ is subject to both human andmechanical error, which in combination can impose an uncertainty ofabout ±0.4° on each reported value of 2θ. This uncertainty is alsotranslated to the reported values of the d-spacings, which arecalculated from the 2θ values. The intensity of each peak was determinedby the peak height after subtracting background. To prevent errors inpeak deconvolution, the background is taken to be linear in the rangedelimiting the broad diffraction features, 6-2 Å. I_(o) is the intensityof the peak at 2θ of 34.5-36.5°. I/I_(o) is the ratio of the intensityof a peak to I_(o). In terms of 100(I/I_(o)), the above designations aredefined as: vw=0-5, w=5-20, m=20-60, s=60-80, and vs=80-100. It is knownto those skilled in the art, the noise/signal ratio in XRD depends onscan conditions. Sufficient scan time is required to minimizenoise/signal ratio to measure peak intensities.

In certain instances, the purity of a synthesized product may beassessed with reference to its x-ray powder diffraction pattern. Thus,for example, if a sample is stated to be pure, it is intended only thatthe x-ray pattern of the sample is free of lines attributable tocrystalline impurities, not that there are no amorphous materialspresent. As will be understood to those skilled in the art, it ispossible for different poorly crystalline materials to yield a Braggreflection at the same position. If a material is composed of multiplepoorly crystalline materials, then the peak positions observedindividually for each poorly crystalline materials would be observed inthe resulting summed diffraction pattern. Likewise it is possible tohave some Bragg reflections appear at the same positions withindifferent, single phase, crystalline materials, which may be simply areflection of a similar distance within the materials and not that thematerials possess the same structure.

EXAMPLE 1

32.4 g of Ammonium Heptamolybdate was dissolved in 200 g DI H2O and setto stir in a beaker. Then, 59.4 g of Ammonium Metatungstate dissolved in200 g DI H2O was added, followed by the addition of 113.4 g of Ni(NO3)2dissolved in 200 g DI H2O to obtain a clear green solution. 19.32 g ofTBABr dissolved in 200 g DI H2O was added and pale green slurry wasobtained. Remaining 280 g DI H2O was then added, followed by theaddition of 120 ml of NH4OH. The pH of the resulting slurry was˜8.68.The slurry was then refluxed at 100° C. for 12 h. The product wasthen cooled, filtered and washed with hot DI H2O, and dried at 110° C.The resulting material was analyzed by x-ray powder diffraction andfound to have an x-ray diffraction pattern comprising the peaks in TableA.

EXAMPLE 2

32.4 g of Ammonium Heptamolybdate was dissolved in 100 g DI H₂O and setto stir in a beaker. Then, 59.4 g of Ammonium Metatungstate dissolved in100 g DI H₂O was added, followed by the addition of 113.4 g of Ni(NO3)2dissolved in 100 g DI H₂O to obtain a clear green solution. 19.32 g ofTBABr dissolved in 100 g DI H₂O was added and pale green slurry wasobtained. Remaining 140 g DI H₂O was then added, followed by theaddition of 142.4 ml of NH4OH. The pH of the resulting slurry was ˜8.75.The slurry was then refluxed at 100° C. for ˜18 h. The product was thencooled, filtered and washed with hot DI H₂O, and dried at 110° C. Theresulting material was analyzed by x-ray powder diffraction and found tohave an x-ray diffraction pattern comprising the peaks in Table A.

EXAMPLE 3

32.37 g of Ammonium Heptamolybdate was dissolved in 200 g DI H₂O and setto stir in a beaker. Then, 58.62 g of Ammonium Metatungstate dissolvedin 200 g DI H₂O was added, followed by the addition of 113.4 g ofNi(NO₃)₂ dissolved in 200 g DI H₂O to obtain a clear green solution.19.33 g of TBABr dissolved in 200 g DI H₂O was added and pale greenslurry was obtained. Remaining 280 g DI H₂O was then added, followed bythe addition of 83 g of NH₄OH. The pH of the resulting slurry was ˜8.The slurry was then digested at 150° C. for 24 h. The product was thencooled, centrifuged and washed with hot DI H₂O, and dried at 110° C. Theresulting material was analyzed by x-ray powder diffraction and found tohave an x-ray diffraction pattern comprising the peaks in Table A.

EXAMPLE 4

32.39 g of Ammonium Heptamolybdate was dissolved in 200 g DI H₂O and setto stir in a beaker. Then, 58.67 g of Ammonium Metatungstate dissolvedin 200 g DI H₂O was added, followed by the addition of 113.49 g ofNi(NO₃)₂ dissolved in 200 g DI H₂O to obtain a clear green solution.19.34 g of TBABr dissolved in 200 g DI H₂O was added and pale greenslurry was obtained. Remaining 280 g DI H₂O was then added, followed bythe addition of 73 g of NH₄OH. The slurry was then digested at 100° C.for 18h. The product was then cooled, centrifuged, and washed with hotDI H₂O, and dried at 110° C.The resulting material was analyzed by x-raypowder diffraction and found to have an x-ray diffraction patterncomprising the peaks in Table A.

SPECIFIC EMBODIMENTS

While the following is described in conjunction with specificembodiments, it will be understood that this description is intended toillustrate and not limit the scope of the preceding description and theappended claims.

A first embodiment of the invention is a mixed transition metal oxidematerial having the formula (M_(I) ^(a))_(m)(M_(I) ^(b))_(n)(M_(III)^(c))_(o)O^(e) _(q) where M_(I) is a metal or a mixture of metalsselected from Group VIII (IUPAC Groups 8, 9, and 10); M_(II) is a metalselected from Group VIB (IUPAC Group 6); M_(III) is a metal selectedfrom Group VIB (IUPAC Group 6) which is different from M_(II); a, b, c,and e are the valence state of M_(I), M_(II), M_(III), and O; m, n, o,and q are the mole ratio of M_(I), M_(II), M_(III), and O, whereinm/(n+o) is from 1/10 to 10/1, wherein n/o>0 and 0≤o/n≤100, wherein q isgreater than 0; and wherein a, b, c, e, m, n, o, and q satisfy theequation a*m+b*n+c*o+e*q=0, the material further characterized by anx-ray diffraction pattern comprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°. An embodiment of the invention is one, any or all ofprior embodiments in this paragraph up through the first embodiment inthis paragraph wherein the mixed transition metal oxide material ispresent in a mixture with at least one binder and wherein the mixturecomprises up to 80 wt % binder. An embodiment of the invention is one,any or all of prior embodiments in this paragraph up through the firstembodiment in this paragraph wherein the binder is selected fromsilicas, aluminas, silica-aluminas, titanias, zirconias, natural clays,synthetic clays, and mixtures thereof. An embodiment of the invention isone, any or all of prior embodiments in this paragraph up through thefirst embodiment in this paragraph wherein M_(I) is Fe, Co, Ni, or anymixture thereof. An embodiment of the invention is one, any or all ofprior embodiments in this paragraph up through the first embodiment inthis paragraph wherein M_(II) is Cr, Mo, or W. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the first embodiment in this paragraph wherein M_(III) is Cr,Mo, or W and is different from M_(II). An embodiment of the invention isone, any or all of prior embodiments in this paragraph up through thefirst embodiment in this paragraph wherein the novel mixed transitionmetal oxide material is sulfided.

A second embodiment of the invention is a method of making a mixedtransition metal oxide material having the formula (M_(I)^(a))_(m)(M_(I) ^(b))_(n)(M_(III) ^(c))_(o)O^(e) _(q) where M_(I) is ametal or a mixture of metals selected from Group VIII (IUPAC Groups 8,9, and 10); M_(II) is a metal selected from Group VI (IUPAC Group 6);M_(III) is a metal selected from Group VI (IUPAC Group 6) which isdifferent from M_(II); a, b, c, and e are the valence state of M_(I),M_(II), M_(III), and O; m, n, o, and q are the mole ratio of M_(I),M_(II), M_(III), and O, wherein m/(n+o) is from 1/10 to 10/1, whereinn/o>0 and 0≤o/n≤100, wherein q is greater than 0; and wherein a, b, c,e, m, n, o, and q satisfy the equation a*m+b*n+c*o+e*q=0, the materialfurther characterized by an x-ray diffraction pattern comprising thepeaks in Table A:

TABLE A 2θ (°) d(Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°; the method comprising forming a reaction mixturecontaining a protic solvent, sources of M_(I), M_(II), and M_(III), abasic solution, and at least one short-chain alkyl quaternary ammoniumhalide compound having the formula [R1 R2 R3 R4-N]X, where R1, R2, R3and R4 are alkyl radicals having 1 to 6 carbon atoms, and R1, R2, R3 andR4 can be the same or different; (a) mixing the reaction mixture; (b)reacting the reaction mixture at a temperature from about 25° C. toabout 200° C. for a period of time from about 30 minutes to 200 hours togenerate the mixed transition metal oxide material; and (c) recoveringthe mixed transition metal oxide material. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the second embodiment in this paragraph wherein the recoveringis by decantation, filtration or centrifugation. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the second embodiment in this paragraph further comprisingadding a binder to the reaction mixture or to the recovered mixedtransition metal oxide material. An embodiment of the invention is one,any or all of prior embodiments in this paragraph up through the secondembodiment in this paragraph wherein the binder is selected fromaluminas, silicas, alumina-silicas, titanias, zirconias, natural clays,synthetic clays, and mixtures thereof. An embodiment of the invention isone, any or all of prior embodiments in this paragraph up through thesecond embodiment in this paragraph further comprising sulfiding atleast a portion of the recovered mixed transition metal oxide material.An embodiment of the invention is one, any or all of prior embodimentsin this paragraph up through the second embodiment in this paragraphfurther comprising adjusting the pH of the reaction mixture using anacidic or a basic solution. An embodiment of the invention is one, anyor all of prior embodiments in this paragraph up through the secondembodiment in this paragraph wherein the reacting is conducted underatmospheric pressure or autogenous pressure. An embodiment of theinvention is one, any or all of prior embodiments in this paragraph upthrough the second embodiment in this paragraph wherein the forming thereaction mixture and the mixing are at the same time. An embodiment ofthe invention is one, any or all of prior embodiments in this paragraphup through the second embodiment in this paragraph further comprisingmixing during the reacting. An embodiment of the invention is one, anyor all of prior embodiments in this paragraph up through the secondembodiment in this paragraph further comprising intermittent mixingduring the reacting. An embodiment of the invention is one, any or allof prior embodiments in this paragraph up through the second embodimentin this paragraph wherein the temperature is varied during the reacting.

A third embodiment of the invention is a conversion process comprisingcontacting a material with a sulfiding agent to convert at least aportion of the material to metal sulfides and contacting the metalsulfides with a feed at conversion conditions to generate at least oneproduct, wherein the material comprises a mixed transition metal oxidematerial having the formula (M_(I) ^(a))m(M_(II) ^(b))_(n)(M_(III)^(c))_(o)O^(e) _(q) where M_(I) is a metal or a mixture of metalsselected from Group VIII (IUPAC Groups 8, 9, and 10); M_(II) is a metalselected from Group VIB (IUPAC Group 6); M_(III) is a metal selectedfrom Group VIB (IUPAC Group 6) which is different from M_(II); a, b, c,and e are the valence state of M_(I), M_(II), M_(III), and O; m, n, o,and q are the mole ratio of M_(I), M_(II), M_(III), and O, whereinm/(n+o) is from 1/10 to 10/1, wherein n/o>0 and 0≤o/n≤100, wherein q isgreater than 0; and wherein a, b, c, e, m, n, o, and q satisfy theequation a*m+b*n+c*o+e*q=0, the material further characterized by anx-ray diffraction pattern comprising the peaks in Table A:

TABLE A 2θ (°) d (Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.52.460-2.598 vs 53-55 1.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.51.485-1.576 vw 62.8-63.8 1.458-1.478 mwherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°. An embodiment of the invention is one, any or all ofprior embodiments in this paragraph up through the third embodiment inthis paragraph wherein the conversion process is a hydrocarbonconversion process. An embodiment of the invention is one, any or all ofprior embodiments in this paragraph up through the third embodiment inthis paragraph wherein the conversion process is hydroprocessing. Anembodiment of the invention is one, any or all of prior embodiments inthis paragraph up through the third embodiment in this paragraph whereinthe conversion process is selected from hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking. An embodiment of the invention is one, any or all ofprior embodiments in this paragraph up through the third embodiment inthis paragraph wherein the mixed transition metal oxide material ispresent in a mixture with at least one binder and wherein the mixturecomprises up to about 80 wt % binder.

Without further elaboration, it is believed that using the precedingdescription that one skilled in the art can utilize the presentinvention to its fullest extent and easily ascertain the essentialcharacteristics of this invention, without departing from the spirit andscope thereof, to make various changes and modifications of theinvention and to adapt it to various usages and conditions. Thepreceding preferred specific embodiments are, therefore, to be construedas merely illustrative, and not limiting the remainder of the disclosurein any way whatsoever, and that it is intended to cover variousmodifications and equivalent arrangements included within the scope ofthe appended claims.

In the foregoing, all temperatures are set forth in degrees Celsius and,all parts and percentages are by weight, unless otherwise indicated.

1. A mixed transition metal oxide material having the formula:(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)O^(e) _(q) where:M_(I) is a metal or a mixture of metals selected from Group VIII (IUPACGroups 8, 9, and 10); M_(II) is a metal selected from Group VIB (IUPACGroup 6); M_(III) is a metal selected from Group VIB (IUPAC Group 6)which is different from M_(II); a, b, c, and e are the valence state ofM_(I), M_(II), M_(III), and O; m, n, o, and q are the mole ratio ofM_(I), M_(II), M_(III), and O, wherein m/(n+o) is from 1/10 to 10/1,wherein n/o>0 and 0≤o/n≤100, wherein q is greater than 0; and wherein a,b, c, e, m, n, o, and q satisfy the equation:a*m+b*n+c*o+e*q=0 the material further characterized by an x-raydiffraction pattern comprising the peaks in Table A: TABLE A 2θ (°) d(Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.5 2.460-2.598 vs 53-551.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.5 1.485-1.576 vw62.8-63.8 1.458-1.478 m

wherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°.
 2. The mixed transition metal oxide material of claim 1wherein the mixed transition metal oxide material is present in amixture with at least one binder and wherein the mixture comprises up to80 wt % binder.
 3. The mixed transition metal oxide material of claim 2wherein the binder is selected from silicas, aluminas, silica-aluminas,titanias, zirconias, natural clays, synthetic clays, and mixturesthereof.
 4. The mixed transition metal oxide material of claim 1 whereinM_(I) is Fe, Co, Ni, or any mixture thereof.
 5. The mixed transitionmetal oxide material of claim 1 wherein M_(II) is Cr, Mo, or W.
 6. Themixed transition metal oxide material of claim 1 wherein M_(III) is Cr,Mo, or W and is different from M_(II).
 7. The mixed transition metaloxide material of claim 1 wherein the novel mixed transition metal oxidematerial is sulfided.
 8. A method of making a mixed transition metaloxide material having the formula:(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)O^(e) _(q) where:M_(I) is a metal or a mixture of metals selected from Group VIII (IUPACGroups 8, 9, and 10); M_(II) is a metal selected from Group VI (IUPACGroup 6); M_(III) is a metal selected from Group VI (IUPAC Group 6)which is different from M_(II); a, b, c, and e are the valence state ofM_(I), M_(II), M_(III), and O; m, n, o, and q are the mole ratio ofM_(I), M_(II), M_(III), and O, wherein m/(n+o) is from 1/10 to 10/1,wherein n/o>0 and 0≤o/n≤100, wherein q is greater than 0; and wherein a,b, c, e, m, n, o, and q satisfy the equation:a*m+b*n+c*o+e*q=0 the material further characterized by an x-raydiffraction pattern comprising the peaks in Table A: TABLE A 2θ (°) d(Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.5 2.460-2.598 vs 53-551.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.5 1.485-1.576 vw62.8-63.8 1.458-1.478 m

wherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°; the method comprising: (a) forming a reaction mixturecontaining a protic solvent, sources of M_(I), M_(II), and M_(III), abasic solution, and at least one short-chain alkyl quaternary ammoniumhalide compound having the formula [R1 R2 R3 R4-N]X, where R1, R2, R3and R4 are alkyl radicals having 1 to 6 carbon atoms, and R1, R2, R3 andR4 can be the same or different; (b) mixing the reaction mixture; (c)reacting the reaction mixture at a temperature from about 25° C. toabout 200° C. for a period of time from about 30 minutes to 200 hours togenerate the mixed transition metal oxide material; and (d) recoveringthe mixed transition metal oxide material.
 9. The method of claim 8wherein the recovering is by decantation, filtration or centrifugation.10. The method of claim 8 further comprising adding a binder to thereaction mixture or to the recovered mixed transition metal oxidematerial.
 11. The method of claim 10 wherein the binder is selected fromaluminas, silicas, alumina-silicas, titanias, zirconias, natural clays,synthetic clays, and mixtures thereof.
 12. The method of claim 8 furthercomprising sulfiding at least a portion of the recovered mixedtransition metal oxide material.
 13. The method of claim 8 furthercomprising adjusting the pH of the reaction mixture using an acidic or abasic solution.
 14. The method of claim 8 wherein the reacting isconducted under atmospheric pressure or autogenous pressure.
 15. Themethod of claim 8 wherein the forming the reaction mixture and themixing are at the same time.
 16. The method of claim 8 furthercomprising mixing during the reacting.
 17. The method of claim 8 furthercomprising intermittent mixing during the reacting.
 18. The method ofclaim 8 wherein the temperature is varied during the reacting.
 19. Aconversion process comprising contacting a material with a sulfidingagent to convert at least a portion of the material to metal sulfidesand contacting the metal sulfides with a feed at conversion conditionsto generate at least one product, wherein the material comprises a mixedtransition metal oxide material having the formula:(M_(I) ^(a))_(m)(M_(II) ^(b))_(n)(M_(III) ^(c))_(o)O^(e) _(q) where:M_(I) is a metal or a mixture of metals selected from Group VIII (IUPACGroups 8, 9, and 10); M_(II) is a metal selected from Group VIB (IUPACGroup 6); M_(III) is a metal selected from Group VIB (IUPAC Group 6)which is different from M_(II); a, b, c, and e are the valence state ofM_(I), M_(II), M_(III), and O; m, n, o, and q are the mole ratio ofM_(I), M_(II), M_(III), and O, wherein m/(n+o) is from 1/10 to 10/1,wherein n/o>0 and 0≤o/n≤100, wherein q is greater than 0; and wherein a,b, c, e, m, n, o, and q satisfy the equation:a*m+b*n+c*o+e*q=0 the material further characterized by an x-raydiffraction pattern comprising the peaks in Table A: TABLE A 2θ (°) d(Å) 100(I/I₀)  8-14  6.320-11.043 vw 34.5-36.5 2.460-2.598 vs 53-551.668-1.726 s-vs 55-58 1.589-1.668 w-m 58.5-62.5 1.485-1.576 vw62.8-63.8 1.458-1.478 m

wherein the peak at 2θ (°) of 55-58 has a full width at half maximumlarger than 3°.
 20. The process of claim 19 wherein the conversionprocess is a hydrocarbon conversion process.
 21. The process of claim 19wherein the conversion process is hydroprocessing.
 22. The process ofclaim 19 wherein the conversion process is selected fromhydrodenitrification, hydrodesulfurization, hydrodemetallation,hydrodesilication, hydrodearomatization, hydroisomerization,hydrotreating, hydrofining, and hydrocracking.
 23. The process of claim19 wherein the mixed transition metal oxide material is present in amixture with at least one binder and wherein the mixture comprises up toabout 80 wt % binder.